文献类型：期刊文献

英文题名：Operando *OH Tracking Unveils Heteroatom-Tailored Co3O4 Spinel Catalyst for Industrial-Level Current Density Ethylene Glycol Electrooxidation

作者：Jiang, Wenhan[1,6];Liu, Ji Kai[2];Zhou, Hang[3,4,5];Huang, Ze Jiang[3,4,5];Wu, Yi Xiao[2];Cao, Shiyu[1,6];Yang, Du Xiao[2];Wang, Xue Lu[3,4,5];Liu, Peng Fei[2];Zhou, Yi[1,6]

机构：[1]East China Univ Sci & Technol, Sch Resources & Environm Engn, State Environm Protect Key Lab Environm Risk Asses, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Mat Sci & Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China;[3]East China Normal Univ, Sch Phys & Elect Sci, Phys Dept, Shanghai 200241, Peoples R China;[4]East China Normal Univ, Sch Phys & Elect Sci, Shanghai Key Lab Magnet Resonance, Shanghai 200241, Peoples R China;[5]East China Normal Univ, Inst Magnet Resonance & Mol Imaging Med, Shanghai 200241, Peoples R China;[6]Minist Educ, Engn Res Ctr Resource Utilizat Carbon Containing W, Shanghai 200237, Peoples R China

年份：2025

卷号：15

期号：21

起止页码：18612

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20254419434374);WOS:【SCI-EXPANDED(收录号:WOS:001603088100001)】；

基金：This work was supported by the National Natural Science Foundation of China (No. 22376065), the Science and Technology Commission of Shanghai Municipality (No. 22ZR1418600, No. 25ZR1402129, No. 25DZ3000302, and No. 20DZ2250400). The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for help with the characterization. The authors also thank Shanghai Aitins Technology Co., Ltd. for their support and assistance in first-principles calculations.

语种：英文

外文关键词：heteroatom doping; molecular-level mechanism; nucleophile electrooxidation; operando *OHtracking; spinel oxides

摘要：Nucleophile electrooxidation-assisted hydrogen production embodies an efficient strategy that produces energy-efficient hydrogen energy and value-added products. However, conventional anodic catalysts, with single reactive sites, often face challenges like sluggish oxidation kinetics, electrode corrosion, etc. A Ni1.2Cu0.6Co1.2O4 catalyst with multiple reactive sites was synthesized via Ni, Cu heteroatom modulation of spinel Co3O4. An applied potential of 1.34 V versus reversible hydrogen electrode was applied to achieve 100 mA cm-2 for the ethylene glycol electrooxidation reaction (EGOR), which was reduced by 250 mV compared to that required for the oxygen evolution reaction, with formate identified as the primary EGOR product. Additionally, the Ni1.2Cu0.6Co1.2O4/Ni foam catalyst was applied as an anode in a membrane electrode assembly flow electrolyzer, demonstrating operational stability exceeding 170 h at 300 mA cm-2. The substitution of Co3+(Oh) and Co2+(Td) with Ni3+ and Cu2+, respectively, facilitated synergistically enhanced specific adsorption of nucleophiles and hydroxyl radicals (*OH) as well as nucleophile oxidation reaction kinetics. Using ethylene glycol as a model molecule, operando nuclear magnetic resonance and Fourier transform infrared spectroscopy realized operando *OH tracking and EGOR intermediate determination, revealing the *OH transfer pathway in both EG dehydrogenation and product synthesis processes, providing in-depth insight into the reaction mechanism of EGOR.